Method of producing sodium aluminum hydrides



United States Patent US. Cl. 260-448 3 Claims ABSTRACT OF THE DISCLOSURE Method for making sodium aluminum hydrides of the general formula Na AlH Z wherein x is an integral number between 1 and 4, inclusive, and n is 0, or wherein x is 6 and n is 2, and wherein Z is an organic rest derived by splitting off an active atom, such as hydrogen, from an organic compound. Regarding this latter compound, reference is made to the specification. At least one compound selected from the group consisting of NaAlZ A12 ZH, NaAlH Z A1HZ and AlH Z, wherein y is an integral number between 1 and 3, inclusive, and is different from x, and wherein z has the meaning as above, is reacted, under hydrogen pressure, with aluminum and at least one substance selected from the group consisting of sodium, NaZ and sodium hydride.

For instance, NaAlH (OCI-l Cl-l OCH is produced by reacting aluminum with sodium and The sodium aluminum hydrides are valuable as reducing and dehalogenating agents.

CROSS-REFERENCES TO RELATED APPLICATIONS Another method of making substituted sodium aluminum hydrides has been disclosed and claimed in application Ser. No. 594,971, of Jaroslav Vit et al., filed Nov. 10, 1966, and assigned to the same assignee as the present case.

The present application is a continuation-in-part of application Ser. No. 611,845, filed Jan. 26, 1967, now abandoned, and assigned to the same assignee as the present application.

BACKGROUND OF THE INVENTION Certain organically substituted sodium aluminum hydrides, for instance sodium aluminum alkoxy hydrides and sodium aluminum aryloxyhydrides, are known and used as specific reducing agents in organic chemistry. It is possible, for instance, by using these compounds as reducing agents to reduce aldehydes, ketones and organic acid esters and chlorides to alcohols, to reduce nitrocompounds to amines and nitriles to aldehydes, Furthermore, these compounds are useful as dehalogenating agents.

Various processes have been described for producing these compounds. One process for obtaining substituted sodium aluminum hydrides has been described in application Ser. No. 594,971, filed Nov. 10, 1966.

One of the difficulties encountered in producing the above-described compounds is that they are not prepared from basic reactants, i.e. from aluminum and sodium.

It is therefore an object of the present invention to overcome the above-mentioned difiiculty.

It is a further object of the present invention to provide a method of producing organically substituted sodium aluminum hydrides which can be carried out in a simple and economical manner starting from the basic reagents, i.e. from aluminum, sodium and hydrogen.

It is yet another object of the present invention to provide a method for producing non-substituted sodium aluminum hydrides of the general formula Na AlH wherein n is zero or two, through which method the said hydrides are obtained in mixture with organically substituted sodium aluminum hydrides of the formula NaAlH Z wherein x is an integral number between 1 and 3 inclusive.

-It is an additional object of the present invention to provide a method for the direct synthesis of non-substituted sodium aluminum hydrides, particularly of sodium aluminum tetrahydride and trisodium aluminum hexahydride without use of a catalyst, in which method the simultaneously proceeding direct synthesis of the present invention of organically substituted sodium aluminum hydrides serves as a promoter of the direct synthesis of non-substituted sodium aluminum hydrides.

It is still another object of the present invention to provide a method for the direct synthesis of organically substituted sodium aluminum hydrides of the formula NaA1I-I Z wherein x is an integral number between 1 and 3, inclusive, and a method for producing non-substituted sodium aluminum hydrides of the general formula Na AlH wherein n is zero or two, wherein the latter hydrides are obtained in mixture with the said substituted sodium aluminum hydrides of the formula NaAlH Z wherein x is an integral number between 1 and 3, inclusive, in an organic aprotic solvent.

SUMMARY OF THE INVENTION With the above and other objects in view, the present invention contemplates a method of producing sodium aluminum hydrides of the general formula wherein x is an integral number between 1 and 4, inclusive, and n is zero, or, wherein x is 6 and n is 2, and Z is selected from the group consisting of Y, Q, and W, wherein Y is an organic rest derived by splitting 01f an active hydrogen atom from a compound selected from the group consisting of:

(1) alcohols and phenols (2) tetrahydrofurfuryl alcohols (3) ether alcohols obtainable by alkylating one hydroxyl group in diols (4) polyether alcohols of the type obtainable by dehydration of tetrahydrofurfuryl alcohols and diols and wherein Q is an organic rest derived by splitting off an active hydrogen atom from a compound selected from the group consisting of (I) HO (C H Q SR wherein j is an integral number between 1 and 5, inclusive, and s is an integral number between 1 and 3, inclusive, and wherein R is selected from the group consisting of alkyl, aryl, alkoxyalkyl of the type and alkoxyalkyl of the type CH OCH CH and wherein W is an organic rest derived by splitting off an active hydrogen atom from a compound selected from the group consisting of:

(a) tetrahydropyranyl alcohols,

(b) polyether alcohols of the type obtainable by dehydration of tetrahydropyranyl alcohols and diols,

(c) aminoalcohols of the general formula,

R'R"'N(CH OH, wherein R" and R are each selected from the group consisting of alkoxyalkyl of the formula R'O(CH and R, and wherein R is selected from the group consisting of alkyls with 1-4 carbon atoms and aryls with 6-8 carbon atoms and wherein z is an integral number between 2 and 4, inclusive,

(d) polyetheralcohols of the type, obtainable by dehydration of polyglycols and etheralcohols, by dehydration of polyglycols and tetrahydrofurfuryl-alcohols, and by dehydration of polyglycols and tetrahydropyranyl alcohols,

(e) polyetheralcohols, of the type obtainable by alkylation of two hydroxyl groups in triols,

(f) polyetheralcohols of the type obtainable by dehydration of polyetheralcohols of paragraph (e) and diols, and by dehydration of polyetheralcohols of paragraph (e) and polyglycols,

comprising the steps of reacting under hydrogen pressure at least one compound selected from the group consisting of NaAlZ AlZ ZH, NaAlH Z NaAlHZ NaAlH Z, AlHZ and AlH Z, wherein Z has the same meaning as above, with aluminum and at least one substance selected from the group consisting of sodium, NaZ, and sodium hydride.

In another embodiment of the invention, the reaction is carried out, under hydrogen pressure, between aluminum and at least two substances selected from the group consisting of sodium, NaZ and sodium hydride, it being stipulated that at least one of the said substances must be NaZ, Z having the meaning as above. NaZ must be soluble in benzene or another aprotic solvent.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Compounds of the general formula AlZ and NaZ, which may be used as reactants, as will be described in detail further below, may be prepared by the reaction of the respective alcohol with the metal, i.e. with sodium or aluminum, or with the respective hydride, i.e. with sodium hydride or aluminum hydride. There is no difiiculty involved in preparing the thioalkoxy, dialkylamino and alkylarnino substituted derivatives. In the case of the preparation of the thioalcoholates of the'type NaZ and A12 however, it is recommended to start from the more reactive hydrides NaH and AlH instead of the metals.

The reactions, generally, may be carried out in liquid media, such as hydrocarbons, ethers (diethyl ether, monoglyme, tetrahydrofurane) using an excess of the ZH compounds, so as to prepare the NaZ and A12 compounds in satisfactory yields.

The thus formed NaZ compounds are insoluble in the reaction medium and thus will be formed as a suspension.

The thus formed suspension in a liquid reaction medium may be used directly as a mixture of NaZ and ZH or AlZ and ZH, respectively, without any further purification or isolation, for the direct synthesis of the present invention; in the case of the preparation of the NaZ and A12 compounds, without excess of the ZH compound, atomic metal, i.e. sodium or aluminum will be in the liquid reaction mixture. The presence of these metals in said reaction mixture is of no inconvenience in the preparation of the sodium aluminum hydrides of the formula Na AlH Z according to the present invention, since they represent one of the reactants. Thus, the crude reaction mixture obtained from the preparation of NaZ or A12 may be used for carrying out the invention, so that the isolation of NaZ and A12 seems rather unnecessary.

Another advantageous method of producing aluminum alcoholates and thioalcoholates of the type AlZ is based on the following equilibrium reactions:

(1) Al(OCH +ZH@AIZ +3CH OH (2) Al(OR +ZHZ AlZ +3ROH wherein R is the same as above. It is advisable to use an excess of ZH and to cary out the reaction under simultaneous removal of CH OH or ROH, the boiling point of which must be lower than that of ZH, which usually will be the case. The stripping off of the CH OH or ROH may be conveniently carried out by using a rectification column. The starting aluminum alcoholates to carry out the reactions (1) and (2) are easily accessible in a pure state, even on an industrial scale. To start from Al(OCH seems to be most advantageous, since the same is insoluble, e.g. in hydrocarbons, thus faciiltating the separation of any unaltered portion thereof from the reaction mixture. The product AlZ may be isolated by simply stripping off the ROH and the excess of ZH.

The starting compound of the type NaAlZ may be prepared by the reactions accounted for as below:

The complex alcoholates of the type NaAlZ are generally easily soluble in ethers and some of them even in aromatic hydrocarbons.

The alcoholates of the type NaAlZ may also be readily prepared by addition of NaZ to A12 in a medium, in which at least one of the compounds A12 and NaZ is soluble.

The preparation of the compounds of the type AlH Z and AlHZ wherein Z is alkoxy or aroxy is described in German Patent 1,085,515 and in a similar manner, all compounds of the type A1HZ and AlH Z may be prepared, which form an element of the reaction of the present invention such as:

There is, of course, another way to prepare compounds of the type AIH Z and AlHZ which is shown by the following equation:

9) A1H+qZH Arum-awn,

Another feature of the present invention is the possibility of converting the compounds of the type NaAlH Z wherein y x=1, 2 or 3 into the compounds of the general formula Na AlH Z wherein x#y, but otherwise has the same meaning as above, and wherein Z and it each have the same meaning as above.

Some methods of preparation of the starting compounds of the type NaAlH Z are disclosed in the German patent 1,085,515, and are also described in US. application Ser. No. 594,971.

The method of the present invention may be carried out in accordance with any of the following equations to 53, on the assumption that in said equations the number of moles of Al, Na, NaZ or NaH, respectively, is greater than zero, or, in the case of adding two or more of the equations together, on the assumption that EA], ZNa, ZNaZ, ENaH respectively in the thus added equations is greater than zero.

In the Equations 10 to 53, g is any number between zero, inclusive, and fifty times the number of moles of the group Z entering the reaction, preferably between zero, inclusive, and five times the number of moles of the group Z entering the said reaction; x is an integral number between 1 and 3, inclusive. The range of g and x is given on the assumption, again, that the sum of the number of moles, ENa, ZNaH, and ENaZ is greater than zero and that also the number of moles of Al is greater than zero. This is not the case, for instance, if in any of the Equations 10 to 13 x=1 and g=0. However, if Equations 10 to 13 are combined with any of the Equations 1453 that are not excluded if x=1 and g=(), the so added Equations 10 to 13 Will then also be practicable according to this invention and will fall within the scope of the same even though x=1 and g=0. Similarly,, in the Equations 10 to 13 and 31) to 41, the g(x) values must always be chosen to satisfy the basic condition of the present invention, i.e., that at least one of the substances selected from the group consisting of Na, NaH and NaZ, a certain amount of aluminum, and at least one of the compounds selected from the group consisting of A12 NaAlZ ZH, AlH Z, AlHZ and NaAlH Z are present in the reaction mixture (y being the aforementioned conditions are satisfied. The presence of hydrogen under superatmospheric pressure, however, is a necessary condition; the hydrogen present need not necessarily be consumed by the reaction.

As aforementioned, any combination of the Equations 10-53 lies within the scope of the present invention. It is easily understood that it is practically impossible to give .here all possible combinations.

The following example of combining the Equations 14, 31, 42 and 48 together is illustrative only, without, however, limiting the invention to the specific details thereof:

Example XXXVII below was carried out following this equation after insertion of 2 for x and of zero for g.

Various other combinations of the Equations 10 to 53 are specifically carried out and described in Examples VIII, XII, XVI, XXIII, XXXI, and XXXIV, below.

For practical purposes, however, working with one starting reactant only, selected from each of the two respective groups, and with aluminum, seems to be the most convenient procedure. Expressed in other terms, the most simple and suitable manner of carrying out the invention is to use one and only one of the Equations 10 to 53 at the same time. A combination thereof, however, may sometimes prove useful.

Thus, it falls within the scope of the present invention carrying out the reactions 10 to 53 to obtain:

(I) Substituted chemically distinct hydrides NaAlH Z (II) Mixtures of substituted hydrides NaAlH,,Z

(III) Mixtures of substituted hydrides NaAlH Z with non-substituted hydrides, the, latter being selected from the group consisting of Na AlH and NaAlH wherein Z has the same meaning as above and x is an integral number between 1 and 3, inclusive. Whether only substituted dhydrides NaAlH,,Z are obtained, or whether hydrides selected from the group consisting of Na AlH and NaAlH depends primarily on the choice. of the Equations 10 to 53, based on which the reaction is carried out, secondarily on the choice of the values for x and g which are inserted into the selected equation. There are certain equations among Equations 10 to 53 which provided they are not combined with other equationswill yield exclusively mixtures of substituted and nonsubstituted hydrides; preparation of substituted hydrides NaAlH Z only is not practical following these equations.

According to another variation, the present invention is also concerned with carrying out any of the Reactions 10 to 3 or any of their combinations in an aprotic solvent.

The aprotic solvent medium, in which the abovedescribed reactions of the present invention are carried out, is preferably selected from the group consisting of hydrocarbons and ethers; the. preferred aprotic solvent is benzene or toluene, but, however, any of the aprotic solvents described may be used.

A preferred embodiment of the invention comprises carrying out the reaction at a temperature of 80 to 220 C., preferably at 100 to 200 C., and at a hydrogen pressure between 2 and 200 atmospheres.

That the reactions of the present invention and the isolation of the products are subject to conversions of the following type which cannot be prevented must be kept in 8 mind in the interpretation of Equations 10 to 54 and their combinations:

for x=l or 2 and for 0:2 or 3 (c x) forx=l, 2or3 All the substances prepared according to this invention are valuable reducing agents. It is possible, however, and it lies within the scope of this invention, to prepare not only the well-known and described types of alkoxy and aroxy aluminohydrides, but to prepare types that have not yet been described in the literature and which possess the same possibilities of application as the known types.

Some of the novel compounds of the invention are readily soluble in non-polar aprotic solvents, such as aromatic hydrocarbons, whereby the field of their possible application is increased, as has been disclosed in detail in U.S. application 594,971.

The following examples illustrate in detail various embodiments falling within the scope of our invention, and are to be considered as non-limitative.

EXAMPLE I Into a pressure vessel of 2.5 1. volume were charged 18 g. sheet aluminum (as usually used in the preparation of aluminum alcoholates), i.e. 0.66 mol., 46 g. sodium (2 moles), 33.6 g. of Al(OCH CH OCH (i.e. 1.33 moles), and 600 m1. benzene. Eight balls were inserted into the pressure vessel to effect stirring of the reaction mixture. Hydrogen was introduced into the pressure vessel to establish a pressure of atmospheres. The reaction was carried out at C. across 6 hours. Subsequent to filtration, and after evaporation of benzene, 396.3 g. of NaAlH (OCH CH OCH were isolated from the reaction mixture, i.e., 98.1% of the theory.

EXAMPLE II Into the same pressure vessel as described in Example I were charged 350 g. of NaAl(OCH CH OCH i.e. 1 mol, 23 g. of sodium (1 mol), 27 g. of aluminum (1 mol) and 600 ml. of benzene. The reaction was carried out similarly under substantially the same reaction conditions as described in Example 1. Isolation yielded 397.1 g. of NaAlH (OCH CH OCH which corresponds to 98.3% of the theory.

EXAMPLE III NaAlH 2 was isolated, 396.8 g. of the said product obtained, i.e., 98.2% of the theory.

EXAMPLE IV Into a pressure vessel of 2.5 1. volume were charged 20.4 of powdered aluminum of 88.23% purity (containing 11.77% aluminum oxide), 46 g. sodium (2 moles), 387 g. Al(OCH CH N(-CH i.e. 1.33 miles, and 600ml. benzene. Eight balls were inserted into the pressure vessel for stirring of the reaction mixture. Hydrogen was fed into the vessel to establish a pressure of 100 atmospheres. The reaction was then carried out at a temperature of 180 C. for a period of 2 hours. Subsequent to filtration and evaporation of benzene, 443.3 g. of NaAlH [OCH CH N(CH was isolated from the reaction mixture, which corresponds to 98.2% of the theory.

EXAMPLE V The same pressure vessel as in Example IV was charged with 402 g. NaAl[OCH CH N(CH i.e., 1 mol, 23 g. sodium (1 mole), 30.6 aluminum of 88.23% purity (1 mol), and 600 ml. benzene. Under conditions identical to those of Example IV, 443.7 g. of

NaAlH [OCH CH 3 2] 2 which corresponds to 98.3% of the theoretical yield.

EXAMPLE VI Into the same pressure vessel as described in Example IV were charged 46 g. sodium (2 moles), 61.2 g. aluminurn of 88.22% purity (2 moles), containing 11.28% of aluminum oxide, 356 g. (CH NCH CH OH and 600 ml. benzene. A pressure of 50 atmospheres was established in the pressure vessel prior to heating. The pressure vessel was heated for 3 hours, at 180 C. the reaction was discontinued; 422.8 g. of

was isolated, i.e., 98.1% of the theoretical yield.

EXAMPLE VII Into a rotary pressure vessel, as described in Example I, were charged 30.6 g. aluminum powder of 88.23% purity (1 mole), 23 g. sodium (1 mole), 64.1 g. of methyl alcohol (2 moles) and 600 ml. toluene. A stirring bar was inserted into the pressure vessel for stirring the reaction mixture and hydrogen was introduced to establish a pressure of 80 atmospheres. The reaction was carried out at a temperature of 170 C. for a period of 2.5 hours. Toluene was stripped E and 110.8 g. of NaAlH (OCH was extracted with tetraphydrofurane from the reaction mixture, i.e. 97.2% of the theoretical yield.

EXAMPLE VIII Into the pressure vessel as referred to in Example VII were charged 30.6 g. of aluminum powder (88.23% purity), i.e. 1 mole, 46 g. of sodium (2 moles), 138.21 g. ethyl alcohol (3 moles), 162 g. Al(OC H and 600 ml. benzene. Upon treatment of the reaction mixture in the manner described in Example VII, 359.72 g. of NaAlI-I(OC H was obtained, which corresponds to 96.7% of the theoretical yield.

EXAMPLE IX Into the pressure vessel as referred to in Example VII were charged 113.7 g. NaAl[O(CH CH i.e., 0.25 mole, 17.25 of sodium (0.75 mole), 23 g. aluminum powder of 88.23% purity (0.75 mole) and 600 ml. benzeue. Eight steel balls were inserted into the pressure vessel for stirring of the reaction mixture and a pressure of 100 atm was esctablished in the pressure vessel by introduction of hydrogen. The reaction was carried out at 170 C. for a period of 3.5 hours. 149.7 g. of NaAlH O (CH CH was obtained, i.e. 97.1% of the theoretical yield.

EXAMPLE X The pressure vessel as referred to in Example VII was charged with 30.6 g. aluminum powder of 88.23% purity (1 mole), 23 g. of sodium (1 mole), 188.2 g. phenol (2 moles) and 500 ml. benzene. The reaction was carried out at 185 C. for a period of 4 hours, in the manner described in Example VII. Benzene was stripped off, and 225.1 g.

was obtained, i.e., 94.5% of the theoretical yield.

EXAMPLE XI The pressure vessel referred to in Example VII was charged with 23 g. sodium, 30.6 g. aluminum powder of 88.23% purity (1 mole), 216 g. p-cresol (2 moles). The reaction and isolation was carried out in the manner described in Example X; 255 g. of NaAlH (OC H CH was isolated, i.e., 95.8% of the theoretical amount of the product was recovered.

EXAMPLE XII The pressure vessel as referred to in Example VII was charged with11.5 g. sodium (0.5 mole), 15.3 g. aluminum powder of 88.23% purity (0.5 mole), 62 g. of

LO CI-DONQ.

(0.5 mole), 165 g. of

and 600 ml. toluene. Under conditions identical with those described in Example X,

NaAlH l was prepared and 249 g. of the product recovered, i.e., 98% of the theoretical yield.

EXAMPLE XIII Into the pressure vessel referred to in Example VII, 23 g. sodium (1 mole), 30.6 g. aluminum powder of 88.23% purity (1 mole), 152 g. CH OCH CH OH were charged. Eight steel balls were inserted thereinto and hydrogen introduced to estabilsh a pressure of 75 atm. The reaction was carried out at a temperature of 165 C. for a period of 4 hours. The reaction mixture was extracted from the pressure vessel with 700 ml. benzene and the solid residue was filtered off; upon stripping off the benzene, 195 g. of NaAlH (OCH CH OCH was obtained, i.e., 96.5% of the theoretical yield.

EXAMPLE XIV The same pressure vessel as referred to in Example VII was charged with 11.5 g. sodium (0.5 mole), 15.3 g. powdered aluminum of 88.23% purity (0.5 mole), 79.5 g. (0.25 mole) of NaAlH(OCH CH OC H and 600 ml. diglyme; a stirring bar was inserted into the pressure vessel and hydrogen introduced to establish a pressure of atm; the vessel was heated to C. for a period of 3 hours. The solid residue was filtered off and diglyme was stripped off in vacuo to recover the resulting NaAlH OCH CH OC H The product was obtained in an amount of 104.7 g., i.e.., 98.3% of the theoretical yield.

EXAMPLE XV Into the pressure vessel referred to in Example VII, were charged 11.5 g. sodium (0.5 mole), 15.3 powdered aluminum of 88.23% purity (0.5 mole), 87 g.

NaO omomo (0.5 mole), 240 g.

4.1( ooruomo) i.e. 0.5 mole, 600 ml. toluene and a stirring rod. Hydrogen was fed into the pressure vessel to establish the pressure of 75 atm.; the reaction was carried out at 160 C. for a period of 4 hours. Upon extraction with toluene,

335 g. of

mmm oomcmo was obtained, i.e., 94.6% of the theoretical yield.

EXAMPLE XVI Into the pressure vessel referred to in Example VII, there were charged 23 g. sodium (1 mole), 30.6 g. powdered aluminum of 88.23% purity (1 mole), 312.4 g. CH O(CH OH, i.e. 3 moles, and 600 ml. benzene. The reaction and isolation of the product was carried out in the manner described in Example X; 340 g. of

NaAlH (CH OCH 3 was obtained, i.e. 95 .9 of the theoretical yield.

EXAMPLE XVII Into the same pressure vessel as referred to in Example VII there 'were charged 15.3 g. powdered aluminum (88.23% purity), i.e. 0.5 mole, 71 g.

NaOCH- CH OCH CH OCH mole), g. i.e., 0.25 mole, 600 ml. benzene and a stirring rod. Hydrogen was fed into the pressure vessel to establish a pressure of 90 atm. The reaction was carried out at 160 C. for a period of 4 hours. Subsequently, benzene was stripped, off; upon extraction with tetrahydrofurane, 210 g. of NaAlH (OCH CH OCH CH OCH was isolated, i.e., the yield amounted to 96.5% of the theoretical.

EXAMPLE XVIII Into a pressure vessel referred to in Example VII were charged 23' g. sodium (1 mole), 30.6 g. powdered aluminum of 88.23% purity (1 mole), 360 g. of monomethylether of diethyleneglycol (3 moles) and 8 steel balls. Hydrogen was introduced into the vessel to establish a pressure of 90 atm. The reaction was carried out at 180 C. for a period of 4.5 hours. Subsequent to extraction with 1000 ml. of tetrahydrofurane, the solid residue was filtered off and 394 g.

NaAlH OCH CH OCH CH OCH 3 was recovered from the filtrate by stripping olf the sol vent. The yield was 96.5 of the theoretical.

EXAMPLE XIX The pressure vessel referred to in Example VII was charged with 17.25 g. sodium (0.75 mole), 7.65 g. powdered aluminum of 88.23% purity (0.25 mole), 231 g.

Al OCHzCI-IzOCHzU 600 ml. benzene and a stirring rod. Hydrogen was introduced into the vessel to establish a pressure of 75 atm. and the reaction was carried out at 150 C. for a period 12 of 2.5 hours. The solid residue was filtered off and upon stripping off benzene from the filtrate, 250 g.

NaAlHz O OHzOIIzOCHzU was recovered, i.e., 97.5% of the theoretical yield.

EXAMPLE XXI Into the pressure vessel referred to in Example VII were charged 46 g. sodium (2 moles), 30.6 g. powdered aluminum (1 mole), 76 g. monomethylether of ethylene glycol (1 mole) and 8 steel balls (diameters 2.5 cm.). A pressure of atm. hydrogen was established in the pressure vessel by introducing hydrogen. The pressure vessel was heated to C. for 3.5 hours. The reaction mixture was extracted with benzene and, subsequently, benzene was stripped off; 98.5 g.

NaAlH- OCH CH OCH 2 was recovered, i.e. 97.5 of the theoretical yield. From the solid residue, which remained after the extraction and amounted to 58.2 g., 86.1% was Na A1H thus, trisodium aluminum hexahydride was obtained in a 98% yield.

EXAMPLE XXII The pressure vessel, referred to in Example VII, was charged with 69 g. sodium (3 moles), 30.6 g. powdered aluminum of 88.23% purity (1 mole), 294.1 g.

i.e., 1 mole, 118 g. AlH (OCH CH OC H (0.1 mole) and 8 steel balls. Hydrogen was fed into the vessel to establish a pressure of 100 atm. and the reaction mixture was heated to 160 C. for a period of 3.5 hours. Extraction with benzene yielded 448 g. of the product NaAlH OCH CH OC 5 2 which corresponds to 97.4% of the theoretical yield. The subsequent extraction with benzene ga-ve NaAlH in a 96.3% yield; 52 g. of the said by-product was recovered.

EXAMPLE XXIII The pressure vessel referred to in Example VII was charged with 23 g. sodium (1 mole), 30.6 g. aluminum powder of 88.23% purity (1 mole), 284.2 g.

NaA1H [OCH CH N(C2 5)2]z (1 mole), 600 ml. diglyme and a stirring rod. Hydrogen was introduced to establish a pressure of 100 atm. and.

the reaction mixture was heated to 160 C. for a period of 4 hours. The solid residue was filtered 01f and, by stripping off diglyme in vacuo, 330 g. of

NaAlH OCH CH N (C H 2] 3 was recovered, which corresponds to 97.5% of the theoretical yield.

EXAMPLE XXIV The pressure vessel referred to in Example VII was charged with 46 g. sodium (2 moles), 30.6 g. aluminum powder of 88.23% purity (1 mole), 78.75 g. of

NaAlH OCH CH N (CH3 z 1 a i.e. 0.25 mole, and 8 steel balls. Hydrogen was introduced into the vessel to establish a pressure of 85 atm. The reaction was carried out at 160 C. for a period of 2.5 hours. Extraction with tetrahydrofurane yielded 103 g. NaAlH [OCH CH N(CH i.e., 97.4% of the theoretical yield, moreover, 57.4 g. of an insoluble substance was obtained, which contained 86.5% of Na AlH in a yield which corresponded to 97.2% of the theoretical.

13 EXAMPLE XXV The same pressure vessel as referred to in Example VII was charged with 46 g. sodium (2 moles), 30.6 g. aluminum powder of 88.23% purity (1 mole), 89 g. (CH NCH CH OH (1 mole) and 8 steel balls. Hydrogen was introduced into the vessel to increase the pressure to 90 atm. The reaction was carried out at 160 C. for a period of 4 hours Extraction with benzene yielded a solution from which, subsequent to stripping off of henzene, 110 g. of NaAlH [OCII CH N(CH was recovered, i.e. 96.5% of the theoretical yield. Besides, 58.6 g. of solid residue was obtained, containing Na AlH in a yield which corresponds to 96% of the theoretical. The solid residue contained 83.6% of Na AlH EXAMPLE XXVI The same pressure vessel referred to in Example VII was charged with 11.5 g. sodium (0.5 mole), 15.3 g. aluminum powder of 88.23% purity (0.5 mole), 253.6 g.

A] OCHzCHzOCHa- O a i.e., 0.5 mole, 91.5 g.

Na OOHzCHgOOHg-- (0.5 mole, 600 ml. toluene and at stirring rod. Further treatment of the reaction mixture and isolation was the same as in Example XXIX. The reaction yielded 365.3 g.

and isolation was carried out in the manner described in Example X; 188 g. of

NaAlHz 2] 2 was obtained, i.e., 97.8% of the theoretical yield.

EXAMPLE XXVIII The same pressure vessel referred to in Examples I and VII was charged with 23 g. sodium (1 mole), 15.3 g. aluminum powder of 88.23% purity (0.5 mole), 116.1 g.

AlH OOH2CH2N i.e. 0.5 mole, 600 ml. toluene and a stirring rod. Further treatment of the reaction mixture and isolation of the product were the same as in Example XXIX; 150 g. of

CH3 omom was obtained, i.e., 96.7% of the theoretical yield.

EXAMPLE XXIX The same pressure vessel refered to in Example VII was charged with 49 g. NaOCH CH oCH (0.5 mole),

NaA1H (-OCH CH 0CH was obtained, i.e. 98.1% of the theoretical yield.

EXAMPLE XXX The same pressure vessel referred to in 'Example VII was charged with 6 g. sodium hydride (0.25 mole), 7.65 g. aluminum powder of 88.23% purity (0.25 mole), 99.7 g. NaAl(OCH CH CH(CH i.e., 0.25 mole, 600 ml. benzene and a stirring rod. Further treatment of the reaction mixture and isolation of the product were the same as in Example XXIX. The reaction yielded g.

N flAlH2 (CH3 2 i.e., 97.2% of the theoretical.

EXAMPLE XXXI The pressure vessel referred to in Example VII was charged with 24 g. sodium hydride ('1 mole), 30.6 g. aluminum powder of 88.23% purity (1 mole), 600 ml. diglyme and a stirring rod. The pressure vessel was closed and 74.12 g. isobutyl alcohol injected th ereinto. Hydrogen was introduced to establish a pressure of 100 atm. hydrogen; the reaction was carried out at 170 C. for a period of 5 hours. Subsequent to filtering off the solid residue, diglyme was vacuum-stripped oil. The isolation yielded 122 g.

NaAlHa O GHaOH CH3 0H i.e., 96.82% of the theoretical.

EXAMPLE XXXII The pressure vessel referred to in Example VII was charged with 46 g. sodium (2 moles), 15.3 g. aluminum powder of 88.23% purity (0.5 mole), 73 g.

(0.5 mole) and 8 steel balls. The pressure vessel was closed and hydrogen introduced thereinto to establish a pressure of 100 atm. The reaction was carried out at 155 C. for a period of 5 hours. Extraction with tetrahydrofurane yielded 83 g. NaAlH OCH CH OC H -n, i.e., 97.6% of the theoretical yield; the solid residue amounted to 54.8 g. of a solid substance, 89.4% of which Was Na AlH i.e., 96% of the theoretical amount.

EXAMPLE XXXIII Into the pressure vessel referred to in Example VII, 6 g. sodium hydride (0.25 mole), 7.65 aluminum powder of 88.23% purity (0.25 mole), 133.7 g.

2[ 0 2) 15CH3 l 2 i.e. 0.25 mole, 600 ml. benzene and a stirring rod. Further treatment and isolation were the same as in Example XXIX. The reaction yielded g. of

NaA1H 15CH3] i.e., 98.5% of the theoretical.

EXAMPLE XXXIV Into the pressure vessel referred to in Example VII were charged 42.0 g. sodium hydride (1.75 moles), 7.65

g. aluminum powder of 88.23% purity (0.25 mole),

i.e. 0.5 mole, and 8 steel balls. Further treatment of the reaction mixture and isolation were carried out in the manner described in Example XL. The reaction yielded NaAlHz[O omomon1 i.e., 97.7% of the theoretical, and 54 g. of a solid product, insoluble, containing 92.1% of Na AlH i.e., 97.6% of the theoretical yield of the latter compound;

EXAMPLE XXXV Into the pressure vessel referred to in Example VII were charged 72.1 g.

NaO mmr (0.5 mole), 15.3 g. aluminum powder of 88.23% purity (0.5 mole), 61.7 g.

(0.5 mole), 600 ml. benzene and a stirring rod. The reaction was carried out and the product was isolated in the manner described in Example X; 190 g. of

NaAlH OCH CH was obtained, i.e., 96.4% of the theoretical yield.

EXAMPLE XXXVI Into the pressure vessel referred to in Example VII were charged 11.5 g. sodium (0.5 mole), 15.3 g. aluminum powder of 88.23% purity (0.5 mole), 162 g. benzyl alcohol (1.5 moles), 600 ml. benzene and a stirring rod. Eurther treatment of the reaction mixture and subsequent isolation were carried out in the manner described in Example X. The yield was 180 g.

NaAlH(O CH2 a i.e., 96.7% of the theoretical.

EXAMPLE XXXVII The same pressure vessel referred to in Example VII was charged with 11.5 g. sodium (0.5 mole), 15.3 g. aluminum powder of 88.23% purity (0.5 mole), 183.24 g. o-xylenol (1.5 moles), 600 ml. toluene and a stirring rod. Further treatment of the product and procedure of isolation were similar to those described in Example X. The reaction yielded 200 g.

NaAlH(O- a C 3 i.e., 96.5% of the theoretical.

EXAMPLE XXXVHI funnel and a reflux condenser were charged 1200 ml. toluene and 154 g. of n-C H (CH OHa. The reaction mixture was heated to C. and g. of trimethyleneglycol chlorohydrin was added dropwise for a period of 1.5 hours. Subsequently, the reaction mixture was heated for another 4 hours. Upon cooling, the solid residue was filtered off and the filtrate was fractionally distilled. The distillation fraction 126130 C./ 13 mm. Hg yield 85 g. of the desired substance.

EXAMPLE XXXIX Into a 2.5-liter pressure vessel were charged 46 g. sodium (2 moles), 32.9 g. aluminum of 82% purity in powdered form (aluminum contained 18% of aluminum oxide as impurity) and 38 g. CH OC H OH (0.5 mole), 500 ml. benzene and a stirring bar for stirring of the reaction mixture. Hydrogen was fed into the pressure vessel to establish a pressure of atm., and the reaction was carried out at 200 C. for a period of 3 hours. The reaction mixture was filtered off and extracted with tetrahydrofurane; 55.4 g. of NagAlHg was obtained of 88.5% purity, i.e., 96.1% of the theoretical yield. The benzene filtrate contained alkoxyaluminohydrides, which were subsequently used for catalyzing the next synthesis.

EXAMPLE XL The same pressure vessel as described in Example VII was charge with 46 g. sodium (2 moles), 61.2 g. powdered aluminum of 88.23% purity (2 moles), 32 g. of methyl alcohol (1 mole) and 600 ml. benezene. A stirring bar was inserted for stirring of the reaction mixture. Hydrogen was introduced to build up a pressure of 100 atm. The reaction was carried out at 170 C. for a period of 3.5 hours. Benzene was filtered ofl? and 124.5 g. of a mixture of NaAlH OCH and NaAlH, was extracted with tetrahydroufrane from the crude product which corresponds to 95.04% of the theoretical yield.

EXAMPLE XLI The same pressure vessel as described in Example VII was charged with 92 g. sodium (4 moles), 54 g. A1(OC H i.e. 0.33 mole, 51 g. powdered aluminum of 88.23% purity (1.66 moles), 46 g. ethyl alcohol (1 mole) and 500 ml. toluene. The reaction and isolation of the product were carried out in a similar manner as described in Example XLIX. With tetrahydrofurane, 138.2 g. of NaAlH (OC H was extracted from the reaction mixture, i.e., 97.32% of the theoretical yield. The solid extraction residue amounted to 109.5 g., containing 89.51% of Na AlH i.e. 96.1% of the theoretical.

EXAMPLE XLII The same pressure vessel as described in Example VII was charged with 34.5 g. sodium (1.5 moles), 45.9 g. powdered aluminum (88.23%), i.e. 1.5 moles, 45.5 g. NaA1(OC H -n) i.e., (0.1 mole), 90.5 g.

CH3(CH2) 15 i.e., (0.4 mole), 600 m1. diglyme and a stirring bar. The vessel was fed with hydrogen to build up a pressure of 100 atm. and, then, heated to C. for a period of 4.5 hours. Subsequent to filtering on the said residue, the diglyme was stripped off in vacuo; 204.5 g. of mixture was obtained, containing NaAlI-I [O(CH} CH -n], NaAlI-I [O(CH CH -n], and NaAlH which corresponds to 94.6% of the theoretical yield.

EXAMPLE XLIII The pressure vessel as described in Example VII was charged with 92 g. sodium (2 moles), 21.42 g. of powdered aluminum (88.23% purity), i.e., 0.7 mole, 31.25 g. NaAlH[OCH CH CH(CH i.e., 0.1 mole, 24.6 g. aluminum isobutylate (0.1 mole), 600 ml. benzene and a stirring bar. Hydrogen was introduced into the vessel to establish a pressure of 100 atm. and the vessel was heated for 5 hours to C. Subsequently to stripping off of benzene, 60 g. of a mixture was extracted with tetrahydrofurane, consisting of NaAlHz 2] 2 EXAMPLE XLIV The pressure vessel as described in Example VII was charged with 80 g. sodium (3.5 moles), 45.9 g. powdered aluminum of 88.23% purity (1.5 moles), 600 ml. toluene, 37 g. n-butyLalcohol, 37 g. tertiary butyl alcohol and a stirring bar. The reaction and isolation was carried out in a manner similar to that described in Example LII. The extraction with tertrahydrofurane yield 97 g. of NaAlH (OCH CH CH CH [OC(CH 1 which corresponds to 97.8% of the theoretical yield. The insoluble substance which amounted to 108 g. had a 91.6% content of Na AlH followingly, 97% of the theoretical yield of Na AlH was achieved.

EXAMPLE XLV NaAlHi and NaAlHz() i.e. the yield was 95% of the theoretical.

EXAMPLE XLVI The same pressure vessel as described in Example VII, Was charged with 80.5 g. sodium (3.5 moles), 45.9 g. powdered aluminum of 88.23% purity 1.5 moles), 54 g. p-cresol (0.5 mole), 61.1 g. o-xylenol (0.5 mole), 600 ml. toluene and a stirring bar. The reaction and isolation were carried out in a manner similar to that of Example LII; 132 g. was obtained of a mixture containing NaAlHz(O-C'Ha) NaAlHz(O) 1 CH3 cm 2 i.e., 94.2% of the theory and 115 g. of a solid insoluble residue, in which the content of Na AlH amounted to 85.6% i.e., to 96% of the theoretical.

EXAMPLE XLVII The same pressure vessel as described in Example VII was charged with 80.5 g. sodium 3.5 moles), 45.9 g. aluminum powder of 88.23% purity (1.5 moles) and NaAlH3(O CH2) i.e., 0.5 mole, 600 ml. benzene and a stirring bar. The reaction and isolation were carried out in the manner described in Example LII; 156 g. of

NaAlHa o CH2 was obtained, which corresponds to 97.5% of the theory. The insoluble residue amounted to 110 g., the content of Na AlH was 89.5%, i.e., 96% of the theory.

and

, 1s EXAMPLE XLVIII The same pressure vessel as described in Example VII was charged with 80.5 g. sodium (3.5 moles), 45.9 g. aluminum powder of 88.23% purity (1.5 moles), 600 ml. benzene, 122 g. of 2-phenyl-ethanol (1 mole), and a stirring bar. The reaction and isolation were carried out in a manner similar to that of Example LII; 142 g. of

was obtained, i.e., 96.5% of the theory, and 112 g. of a solid insoluble residue, in which the content of Na AlH amounted to 87.9%, i.e. to 96% of the theoretical.

EXAMPLE XLIX cHtUomorr and a stirring bar. The pressure of hydrogen in the pressure vessel was built up to 100 atm., and the vessel was heated to C. for a period of 4.5 hours. Subsequent to filtration of the reaction mixture, toluene was stripped 011 from the reaction mixture and 102 g. of

NaAlHz 0 CH2 ,(QClL-UCHQ recovered, which corresponds to 95.3% of the theoretical. The filtration cake yielded 90 g. of a solid substance, which contained 87.8% of Na AlH i.e., 96.8% of the theoretical.

EXAMPLE L The same pressure vessel as described in Example VII was charged with 46 g. sodium (2 moles), 76.5 g. of aluminum powder of 88.23% purity (2.5 moles), 69 g.

NaOOH 600 ml. benzene, a stirring bar and 58 g.

CH2OH The pressure vessel was fed with hydrogen to build up a pressure of 100 atm, and heated to C. for a period of 4.5 hours. From the reaction mixture, 137 g. of

N aAlHz O C H2- was extracted With benzene, i.e., 97% of the theory; subsequently, 103 g. of NaAL, was recovered with tetrahydrofurane from the extraction residue, which corresponds to 95.3% of the theory.

19 EXAMPLE LI The same pressure vessel as described in Example VII was charged with 11.5 g. sodium (0.5 mole), 98 g.

CH OCH CH ONa (1 mole), 45.9 g. aluminum powder of 88.23% purity (1.5 moles), 600 ml. benzene and a stirring bar. The reaction and isolation were carried out in a manner identical to that of Example LIX; 99 g. of

NaAlH (OCH CH OCH 2 and 52 g. of NaAlH were obtained, i.e., 98% and 96.3% of the theory, respectively.

EXAMPLE LII EXAMPLE LIII The same pressure vessel as described in Example VII was charged with 160 g.

NaO CHzOH2O (1 mole), 12 g. sodium hydride (0.5 mole), 11.5 g. sodium (0.5 mole), 15.3 g. aluminum powder of 88.23% purity (0.5 mole), 600 m1. benzene and a stirring bar. The

reaction and the isolation were carried out in a mannerv similar to that described in Example LVIII; 158 g. of

NaAIH2(O CH2CH2O) was obtained, i.e. 96.9% of the theory, plus 57 g. of a solid insoluble substance containing 85.9% of Na AlH which corresponds to 96% of the theory.

EXAMPLE LIV The same pressure vessel as described in Example VII was charged with 32.2 g. sodium (1.4 moles), 30.6 g. aluminum powder of 88.23% purity (1 mole), 47.2 g.

i.e., 0.4 mole, 600 ml. benzene and a stirring bar. The reaction and the isolation were carried out in the manner described in Example LIX; 44.5 g.

and 62.5 g. NaAlH were obtained, i.e. 96.7% and 96.4%, respectively, of the theoretical yield.

EXAMPLE LV The same pressure vessel as described in Example VII was charged with 25.3 g. sodium (1.1 moles), 30.6 g. aluminum powder of 88.23% purity (1 mole), 26.6 g. AlH(OCH -CH OCH CH OCH (0.1 mole), 600 ml. toluene and a stirring bar. The reaction and the isolation were carried out in the manner described in Example LIX; 28 g. NaAlI-I (OCH CH OCH CH OCH and 52.5 g. NaAlH were obtained, i.e. 96.5% and 97.2%, respectively, of the theoretical yield.

EXAMPLE LVI The same pressure vessel as described in Example VII was charged with 44.6 g. sodium (1.94 moles), 20.2 g. aluminum powder of 88.23% purity (0.66 mole), 14 g. NaAl[O(CH CH O) CH (0.2 mole), 600 ml. benzene and a stirring bar. The reaction and isolation were carried out in a manner identical with that of Example 20 LVIII. The reaction time, however, was prolonged to 5.5 hours; 14.5 g. of NaAlI-I [-O(CH CH O) CH was obtained (95.9% theory), plus 68 g. of a solid insoluble substance, containing 9.4% of Na AlH i.e., 97.2% of the theoretical yield.

EXAMPLE LVII The same pressure vessel as described in Example VII was charged with 25.3 g. sodium (1.1 moles), 33.7 g. aluminum powder of 88.23% (1.1 moles), 600 ml. toluene and 29.2 g.

U-CHzO CHzCHzOH (0.2 mole), and a stirring bar. The reaction and isolation were carried out in a manner identical with that of Example LIX; 33 g. of

NaAlHz O CHzCHzO CHI-U and 52 g. of NaAlI-L, were obtained, i.e. 96.5% and 96.3% of the theory, respectively.

EXAMPLE LVIII The same pressure vessel as described in Example VII was charged with 52.8 g. sodium (2.2 moles), 23.25 g. of aluminum powder of 88.23% purity (0.76 mole), 47.52 g.

i.e., 0.08 mole, 600 ml. toluene, and a stirring bar. The reaction and the isolation were carried out in the manner described in Example LVIII; 47.5 g.

was obtained, i.e., 95.6% of the theory, plus 78 g. f insoluble solid substance, containing 91.6% Na AlH i.e. 97.3% of the theoretical yield.

EXAMPLE LIX The same pressure vessel as described in Example VII was charged with 28.75 g. sodium (1.25 moles), 38.25 g. aluminum powder of 88.23% purity (1.25 moles), 600 ml. benzene 95.1 g. n-C H (OCH CH CH OH, (0.5 mole) and a stirring bar. The reaction and isolation were carried out in the manner described in Example LIX; g. NaAlH [O(CH CH CH O) C H -n] and 52 g. NaAlH were obtained, i.e., 97.5% and 96.3% of the theoretical yield, respectively.

EXAMPLE LX The same pressure vessel as in Example VII was charged with 25.3 g. sodium (1.1 moles), 33.66 g. aluminum powder of 88.23% purity (1.1 mole), 40.2 g.

(0.1 mole), 600 ml. benzene and a stirring bar. The reaction and isolation were carried Out in a similar manner as that described in Example LIX; 44 g.

NaAlH [OCH CH N(CH 2 and 52 g. NaAlH were obtained, i.e. 96.5% and 96.2%, respectively, of the theoretical yields.

EXAMPLE LXI The same pressure vessel as described in Example VII was charged with 64.4 g. sodium (2.8 moles), 30.6 g. aluminum powder 88.23% pure (1 mole), 79.8 g.

NaAlH [OCH CH N(C H 3 (0.2 mole), 600 ml. benzene and a stirring bar. The

N3-A1H2 (C2H5) 2] 2 was obtained, i.e. 97.4% of the theoretical, and 97 g.

22 i.e., 97.9% of the theoretical, and 104 g. NaAlH which corresponds to 96.3% of the theoretical amount.

EXAMPLE LXVI v The same pressure vessel as in Example VII was of a solid insoluble substance, i.e. 91.75% of Na AlI-I charged with 46 g. sodium (2 moles), 18.4 g. aluminum which corresponds to 96.9% of the theory.

EXAMPLE LXII The same pressure vessel as described in Example VII was charged with 25.3 g. sodium (1.1 moles), 33.7 g. aluminum powder 88.23% pure (1.1 moles), 33.4 g.

(CH OCH CH NCH CH OH (0.2 mole), 600 ml. toluene and a stirring rod. The reaction and the isolation were carried out as in Example LIX; 37 g.

NaAlH [OCH CH N(CH CH OCH and 52.5 g. NaAlH were obtained, which amounted to 96.3% and 97.2%, respectively, of the theoretical yield.

EXAMPLE LXIII The same pressure vessel as described in Example VII was charged with 28.75 g. sodium (1.25 moles), 30 g. aluminum powder 88.23% pure (1 mole), 58 g.

600 ml. benzene and a stirring bar. The reaction and isolation were carried out as in Example LVIII. There were obtained: 62.5 g.

NaAlH [OCH- CH N(CH (C H 1 i.e., 97.6% of the theory, and 106.5 g. of an insoluble substance, which contained 92.95% of Na AlH i.e., 97% of the theoretical yield.

EXAMPLE LXIV The same pressure vessel as in Example VII was charged with 85.1 g. sodium (3.7 moles), 39.8 g. aluminum powder 88.23% pure, (1.3 moles), and 45.8 g.

(0.1 mole), 600 ml. toluene and a stirring bar. The reaction and isolation were carried out as in Example LVIII. There were obtained: 50 g.

i.e., 97.6% of the theory, and 127 g. of insoluble substance, which contained 94.2% of Na AlH i.e., 98% of the theoretical yield.

EXAMPLE LXV The same pressure vessel as described in Example VII was charged with 18.2 g.

NaO (CI-11020 CH (0.1 mole), 48.3 g. sodium (2.1 moles), 54.3 g. aluminum powder 88.23% pure (2.1 moles), 50.4 g.

Al O (OH2)2O CH i.e., 0.1 mole, 600 ml. toluene and a stirring bar. The reaction and isolation were carried out as in Example LIX. The yields were: 72.5 g.

powder 88.23% pure (0.6 mole), 18.8 g.

AlHz C4H9n) i.e., 0.2 mole, 600 ml. benzene and a stirring bar. The reaction and isolation were carried out as in Example LVIII. Subsequent to stripping of]? benzene from the reaction mixture, extraction with tetrahydrofurane was carried out, which yielded 32.5 g.

i.e., 96.7% of the theory; the solid extraction residue amounted to 63 g.; 95.2% thereof was Na AlH which corresponds to 98% of the theory.

EXAMPLE LXVII The same pressure vessel as in Example VII was charged with g.

(1 mole), 15.3 g. aluminum powder 88.23% pure (0.5 mole), 11.5 g. sodium (0.5 mole), and 600 ml. benzene. The reaction and isolation were carried out as in Example X. The yield was 207.5 g. of

a manner similar to that of Example LII.

The yields were:

/CHzO CH 113.4 g. NaAlHz O(CHzCHzO)2CH CHaOCHg z i.e., 97.3% of the theoretical, and 54.1 g. of a solid extraction residue, which was found to contain 90.6% of Na AlH i.e. 96.1% of the theoretical yield.

The starting compound:

HO(CHzOHzO)zCH-CH2O CH3 was prepared in the usual manner from CICHzCHaO OHZCHZOH and NaO CIT-(EH20 CH3 CHzO CH3 The present invention is useful also for producing sodium aluminum hydrides of the type described, in connection with the different method of the above-mentioned application Serial No. 594,571 assigned to the same assignee as the instant case. These compounds comprise,

NaAlH; O CH;

wherein R" and R' are each selected from the group consisting of R'O(CH and R, and wherein R is selected from the group consisting of alkyls with 1-4 carbon atoms and aryls with 6-8 carbon atoms, and wherein x is an integer between 1 and 3, inclusive, and z and w are each selected from the group of integers between 2 and 4, inclusive.

Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can by applying current knowledge readily adapt it for various applications without omitting feautres that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.

What is claimed as new and desired to be secured by Letters Patent is set forth in the appended claims:

1. The process of making NaAlH (OCH CH OCI-I comprising hydrogenating sodium, aluminum and (a) Al(OCH CH OCH or (b) NaAl(OCH CH OCH or (c) CH OCH CH OH at an elevated temperature and pressure in an inert aromatic hydrocarbon medium, the molar ratio of sodium to OCH CH OCH in being 1:2.

2. The process of claim 1 wherein said compounds (a) and (b) are formed in situ by reacting ethyleneglycol monomethylether with aluminum or sodium and aluminum.

3. The process of claim 1 wherein the reaction is carried out in the presence of an aromatic monocyclic hydrocarbon compound selected from the group consisting of benzene, toluene, xylene and mixtures of these compounds and wherein the product is isolated as a solution in said aromatic hydrocarbon compound.

References Cited UNITED STATES PATENTS 3,355,262 11/1967 Beaird et a1. 23365 3,357,806 12/1967 Dvorak et a1. 23365 3,361,781 1/1'968 Ziegler et a1. 260448 3,394,158 7/1968 Chini et al. 260-448 OTHER REFERENCES Chemical Abstracts, volume 52, 1958, pp. 10871-72. Day et 211., Organic Chemistry, D. Van Nostrand Co. Inc., New York, 1960, p. 222.

OSCAR R. VERTIZ, Primary Examiner G. O. PETERS, Assistant Examiner US. Cl. X.R. 233 65 

